title: Synthesis of alpha-keto-imides via oxidation of ynamides.
abstract: A de novo preparation of alpha-keto-imides via ynamide oxidation is described. With a number of alkyne oxidation conditions screened, a highly efficient RuO2-NaIO4 mediated oxidation and a DMDO oxidation have been identified to tolerate a wide range of ynamide types. In addition to accessing a wide variety of alpha-keto-imides, the RuO2-NaIO4 protocol provides a novel entry to the vicinal tricarbonyl motif via oxidation of push-pull ynamides, and imido acylsilanes from silyl-substituted ynamides. Chemoselective oxidation of ynamides containing olefins can be achieved by using DMDO, while the RuO2-NaIO4 protocol is not effective. These studies provide further support for the synthetic utility of ynamides.
authors.affiliation: Division of Pharmaceutical Sciences and Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53705, USA. zalrashid@alchemicalresearch.com
authors.forename: Ziyad F
authors.initials: ZF
authors.lastname: Al-Rashid
authors.forename: Whitney L
authors.initials: WL
authors.lastname: Johnson
authors.forename: Richard P
authors.initials: RP
authors.lastname: Hsung
authors.forename: Yonggang
authors.initials: Y
authors.lastname: Wei
authors.forename: Pei-Yuan
authors.initials: PY
authors.lastname: Yao
authors.forename: Renhei
authors.initials: R
authors.lastname: Liu
authors.forename: Kang
authors.initials: K
authors.lastname: Zhao
mesh_terms: D000480:Alkynes / Q000737:chemistry*; D007094:Imides / Q000138:chemical synthesis* / Q000737:chemistry; D007659:Ketones / Q000737:chemistry*; D010084:Oxidation-Reduction; D013379:Substrate Specificity
chemical_list: D000480:Alkynes; D007094:Imides; D007659:Ketones